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Anaerobic Digestion in

Wastewater Treatment

Aerobic Treatment vs Anaerobic Treatment


Aerobic

50 %

Sludge

50 %

CO2

Organic
matter

Oxygen

Aerobic Treatment vs Anaerobic Treatment


Anaerobic

Organic
matter

10 %

90 %

Sludge

Biogas

Aerobic Treatment vs Anaerobic Treatment


Energy balance for anaerobic pretreatment (recycled paper mill)

Complete Aerobic
Treatment
(MJ/ADT)

Combined
AnaerobicAerobic
(MJ/ADT)

Energy Savings
Difference (MJ/ADT)

Energy production
Energy Consumption

0
90

275
20

275
70

Total Balance

- 90

+ 255

+ 345

ADT, air dry ton = 30 kg COD

Basic Aspects in Anaerobic Digestion

Anaerobic Digestion

Hydrolysis
Considered the rate-limiting step during anaerobic digestion of
complex substrates (availability & structure of substrates)
Catalyzed by exoenzymes

CH2OH
HC-O-

CH 2OH
CH
(H 3CO)
H 3CO

CH2OH
O

CH2O C CH CH

CHOH

CHOH

CH 2OH
HC

CHOH

OCH 3

(H 3CO)
H 3CO

CH 2OH
CH

HC

H 3CO

OCH 3

H 3CO
OHC CH O
H C
HOCH 2 2
HC
CH2OH
HC
CH

OCH 3

CHOH

H3CO
O

HC

OCH 3

OH

CH

H 3CO

CH 2

lignin monomers

OH

HO
CH 2OH

CH

HC

[CARBOHYDRATE]-O- CH

CO

H 3CO

OH

OH

OCH3

CHOH

CH 2OH

H 3CO

OH

CH

OCH

HC

OCH3

OCH 3

OH

H 3CO
HOCH 2

HOCH 2
HC

OCH3

OH

OH

CHOH

OCH 3

CHOH

CH2OH
CH
OCH 3

OH

CH

OH

-CH

CH

OH

CHO

CHO

OCH 3
OH [O-C]

lignin polymer

non-biodegradable

OCH3

H3CO

OCH3

OCH3
OH

lignin dimers

biodegradable

OH

Install Primary Clarifiers or not?

Elmitwalli, TA et al. (2000)

Install Primary Clarifiers or not?

Elmitwalli, TA et al. (2000)

Acidogenesis
Large diversity of microorganisms Eubacterium, Clostridium,
Acetovibrio, Bacteroides, etc.
Main products VFA > C2, alcohols, CO2, H2, NH3, H2S
Most acidogens are strict anaerobes, but there are some facultative
playing an important role maintaining [O2] at low levels

Acetogenesis
Reaction
CH3CHOHCOO- + 2H2O Acetate + HCO3- + H+ + 2H2
(Lactate)
CH3CH2CH2COO- + 2H2O 2Acetate + H+ + 2H2
(Butyrate)
CH3CH2OH + H2O Acetate + H+ + 2H2
(Ethanol)
CH3CH2COO- + 3 H2O Acetate + HCO3- + H+ + 3H2
(Propionate)
4CH3OH + 2CO2 3CH3COOH + 2H2O
(Methanol)
2HCO3- + 4H2 + H+ CH3COO- + 4 H2O

Production of acetate & hydrogen


Most thermodynamics unfavorable under standard conditions

G (kJ/mol)
-4.2
+48.1
+9.6
+76.1
-2.9
-70.3

Acetogenesis
Hydrogenotrophic methanogens play a crucial role in acetogenesis as they
keep [H2] very low making reactions to become thermodynamically
favorable
In such a reaction:
aA + bB

cC + dD

[C]c [D]d
G = G + RT Ln ---------------------[A]a [B]b
If hydrogen is one of the products, then keeping [H2] low makes the
reaction to proceed

Acetogenesis
Through the syntrophic interactions between acetogens & methanogens,
[H2] usually remains between 10-4 & 10-6 atm, which makes the reactions
favorable
Very close coordination between acetogenesis and methanogenesis is
required to maintain an efficient process
It is calculated that H2 is consumed in 0.5 seconds within a distance of 0.1
mm, thus syntrophic microorganisms should be attached in biofilms

Methanogenesis
Reaction
CH3COO- + H2O CH4 + HCO3(Acetate)
4H2 + HCO3- + H+ CH4 + 3H2O
(Hydrogen)
4CH3OH 3CH4 + CO2 + 2H2O
(Methanol)
4HCOO- + 2H+ CH4 + CO2 + 2 HCO3Formate

G (kJ/mol)
-31
-135.6
-312
-32.9

70% of methane produced by acetoclastic microorganisms (Methanosaeta sp. & Methanosarcina sp.)
30% produced by hydrogenotrophic microorganisms (Methanothermobacter & Methanobacterium)
Methanol (Methanosarcina sp.) & formate consuming methanogens only significant for wastewaters
containing large amounts of these substrates

Kinetic constants of anaerobic cultures

Cultures

Acidogenic bacteria
Methanogenic Archaea
Combined culture

m35

m26

Ks

(d-1)

(d-1)

mgVSS/
mgCOD

mgCOD/L

2.0
0.4
0.4

0.70
0.14
0.14

0.15
0.03
0.18

200
50
-

Henzen & Harremoes 1982

pH Range in Anaerobic Digestion

Hydrolisis
Acidogenesis
Acetogenesis
Methanogenesis
Acetate
Hydrogen

pH and Buffering Capacity


pH is a key parameter in anaerobic digestion
Sufficient buffer capacity to neutralize changes in pH influent and due to the
production of VFA from acidogenesis
pH-buffer originates from the presence of weak acids & their salts, which are
capable of binding a relatively big amount of H3O+ & OH- in a narrow pH range
HA + H2O

H3O+ + A-

where Ka is given by
[H3O+] [A-]
Ka = ---------------------[HA]
From this we find the following equation for pH:
[A-]
pH = pKa + log --------------[HA]
Maximal buffer capacity at pH = pKa, when [A-] = [HA]

The CO2/HCO3- Buffer


CO2/bicarbonate represents the main pH-buffer system in natural water
environments
The following two equilibria apply:
H2O + CO2
HCO3- + OH-

H2CO3
H2O + CO3-2

HCO3- + H+

(pKa = 6.3)
(pKa = 10.4)

The amount of H2CO3 in solution is directly related to the amount of CO2 in


the gas phase. The distribution between gas and liquid phase is described by
Henrys equation:
CCO2 = KCO2 * P
where:
CCO2 the saturation concentration of CO2 in water (mol/L)
KCO2 absorption coefficient (mol/L.atm)
PCO2 partial pressure (atm)

The CO2/HCO3- Buffer


Absorption coefficient can be calculated as follows:
KCO2 = (H*R*T)-1
where:
H dimensionless factor equal to the conc.gas/conc.liquid ratio at the gasliquid interface (H = 1.2 for CO2)
R gas constant (0.082 L-atm/K-mol)
T temperature (K)
By combining the acid-base equilibrium and Henrys equation, for a known
alkalinity and PCO2, the pH of the water can be predicted:
KCO2* PCO2*Ka
[H+] = ------------------------------[HCO3-]
pH = log [H+]

Other Buffer Systems


Other buffer systems may also be present in biological systems:
H2S + OHH2PO4- + OHNH4+ + OH-

HS- + H2O
HPO4-2 + H2O
NH3 + H2O

(pKa = 6.5)
(pKa = 7.2)
(pKa = 9.25)

However, they contribute only to a minor extent to the total buffer


capacity of the system, as these compounds are usually present at
relatively low concentrations

Required alkalinity in an anaerobic digester as a function of


the digested COD concentration for different pH values

van Haandel et al. 2006

Influence of temperature on the rate of


anaerobic digestion in the mesophilic range

van Haandel et al. 2006